CN109847598A - A kind of superhydrophilic self-cleaning water-oil separationg film and its preparation method and application - Google Patents
A kind of superhydrophilic self-cleaning water-oil separationg film and its preparation method and application Download PDFInfo
- Publication number
- CN109847598A CN109847598A CN201910077498.4A CN201910077498A CN109847598A CN 109847598 A CN109847598 A CN 109847598A CN 201910077498 A CN201910077498 A CN 201910077498A CN 109847598 A CN109847598 A CN 109847598A
- Authority
- CN
- China
- Prior art keywords
- film
- water
- solution
- oil
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention belongs to polymeric material field, it is related to a kind of superhydrophilic self-cleaning water-oil separationg film and its preparation method and application.The present invention provides a kind of superhydrophilic self-cleaning water-oil separationg film, and the water-oil separationg film is the Modified Membrane that membrane surface is covered with super-hydrophilic coating formation；The super-hydrophilic coating is that plant polyphenol reacts the super-hydrophilic coating to form the coordinate bond of titanium containing carboxylic acid with TiO 2 precursor；The basement membrane is the polymer film or non-polymer film that can be used for water-oil separating.Gained water-oil separationg film of the invention is Superhydrophilic, obtained membrane material can the oil-in-water emulsion stable to a variety of grease stratified mixtures, surface-active quickly and effectively separate；Simultaneously under UV illumination, the photocatalytic degradation characteristic of titanium dioxide makes film have excellent automatically cleaning anti-pollution, i.e., the film of institute is with good multi-cycle separation performance.
Description
Technical field
The invention belongs to high molecular materials and field of environment engineering, and in particular to a kind of superhydrophilic self-cleaning of pure green is anti-
Sump oil water seperation film and preparation method thereof.
Background technique
Daily life and industrial production and frequent Oil spills cause great pollution to water resource, seriously endanger
The ecosystem and human health.Oil water mixture is divided into three classes, and grease is layered solution (drop size is greater than 150 μm), without table
Face activating agent stablizes (drop size is between 20-150 μm) and the stable Water-In-Oil and oil-in-water emulsion of surfactant.Now
Routine techniques for water-oil separating includes absorption, skimming, centrifugation and situ combustion.Although these methods be it is useful, have
Many limitations: (1) it is only capable of handling sticky oiliness water or unmixing oil/water mixture, there is very low effect to oil/water lotion
Rate；(2) cumbersome and have very big negative effect to the ecosystem.Therefore efficient, energy conservation, cost are controllable again green simultaneously
Ground, which handles these oil water mixtures, becomes a big research hotspot of high molecular material and field of environment engineering.
Summary of the invention
The present invention is intended to provide a kind of super hydrophilic antifouling, the automatically cleaning film of pure green, gained film may be implemented mixed to grease
It closes object to efficiently separate, while under UV illumination using the photocatalysis performance of titanium dioxide when keeps greasy dirt degradation to realize good
Anti-pollution.
Technical solution of the present invention:
The invention solves first technical problem be to provide a kind of superhydrophilic self-cleaning water-oil separationg film, the grease
Seperation film is the Modified Membrane that membrane surface is covered with super-hydrophilic coating formation；Wherein, the super-hydrophilic coating is plant polyphenol and two
The super-hydrophilic coating of the titania precursor precursor reactant formation coordinate bond of titanium containing carboxylic acid；The basement membrane is the polymerization that can be used for water-oil separating
Object film or non-polymer film.
Further, the plant polyphenol is the plant polyphenol that ester exchange reaction can occur with TiO 2 precursor；More
Further, the plant polyphenol is the plant polyphenol containing carboxyl；Further, the plant polyphenol includes but is not limited to tannin
Acid, tea polyphenols vine polyphenol or gallic acid.
Further, the TiO 2 precursor includes but is not limited to butyl titanate, ethyl alcohol titanium salt or isopropanol titanium salt.
Further, the super-hydrophilic coating is made using following methods: by plant polyphenol solution and TiO 2 precursor
Solution uniformly mixes at 20~40 DEG C, after reacting 5~30h, by reaction solution using existing coating method in membrane surface shape
At coating；Wherein, the mass ratio of plant polyphenol and TiO 2 precursor is 1:4~10:1.
Further, the super-hydrophilic coating uses following methods to be made: by concentration for the plant polyphenol of 2~8mg/mL
Tris solution and concentration be the alcoholic solution of 0.1~10mg/mL TiO 2 precursor with the volume ratio of 1:1~10:1 20~
It is uniformly mixed at 40 DEG C, after reacting 5~30h, reaction solution is formed into coating in membrane surface using existing coating method.
Further, existing coating method is dip coating, spray coating method or spin-coating method.
Preferably, volume ratio 1:1~8:1 of the alcoholic solution of the Tris solution and TiO 2 precursor of plant polyphenol,
More preferably 4:1.
Further, the polymer film that water-oil separating can be used for be polylactic acid membrane, polyvinylidene fluoride film, polypropylene screen or
Person's cellulose filter membrane etc.；The non-polymer film that can be used for water-oil separating is the metal meshes such as copper mesh, iron net.
Preferably, the basement membrane is polylactic acid membrane；It is furthermore preferred that the basement membrane is l-lactic acid (PLLA) and dextrorotation is poly-
The stereocomplex PLA film that the mixed solution of lactic acid (PDLA) is formed by electrostatic spinning.
Further, the stereocomplex PLA film the preparation method comprises the following steps: first that l-lactic acid and dextrorotation polylactic acid is molten
Mixed solution is formed in solvent, then passes through method of electrostatic spinning for above-mentioned solution electrospinning into tunica fibrosa；Wherein, the work of electrostatic spinning
Skill condition are as follows: the voltage of electrostatic spinning is 5~30kV, and the distance of spinning syringe needle to receiving device is 5~20cm；Preferably, quiet
The voltage of Electrospun is 10~20kV, and the distance of spinning syringe needle to receiving device is 8~18cm.
Further, the solvent be methylene chloride, chloroform, hexafluoroisopropanol or n,N-Dimethylformamide at least
It is a kind of；It is furthermore preferred that mixed solvent of the solvent for methylene chloride and hexafluoroisopropanol, methylene chloride and hexafluoroisopropanol
Volume ratio is 1:9~9:1, and preferred volume ratio is 1:7~7:1, more preferably 2:7~4:7.
Further, the mass ratio of the l-lactic acid and dextrorotation polylactic acid is 1:9~9:1, preferably 1:5~5:1,
It is more preferably 1:1.5~3:1.
The superhydrophilic self-cleaning water-oil separationg film is super hydrophilic and the oil-stain-preventing under UV illumination.
Second technical problem to be solved by this invention is to provide the preparation of above-mentioned superhydrophilic self-cleaning water-oil separationg film
Method, the preparation method is that: plant polyphenol solution and TiO 2 precursor solution hybrid reaction are first obtained into titanium containing carboxylic acid
The reaction solution of coordinate bond, then reaction solution is formed into super-hydrophilic coating in membrane surface using the method for existing coating；Then through washing
It washs, dry to obtain superhydrophilic self-cleaning water-oil separationg film.
Further, when the basement membrane is stereocomplex PLA film, plant polyphenol is gallic acid (GA), before titanium dioxide
Drive body be butyl titanate (TBT) when, the preparation method is that: by concentration be 2~8mg/mL plant polyphenol Tris solution with it is dense
The TiO 2 precursor solution that degree is 1~5mg/mL uniform hybrid reaction 5 at 20~40 DEG C with the volume ratio of 1:1~10:1
~30h obtains reaction solution；Again by basement membrane submergence in the reaction solution reaction 12~be modified processing for 24 hours；Then at will be modified
The basement membrane of reason is dried under 50~70 DEG C (preferably 60 DEG C) with after distilled water flushing at least 1h；It is multiple to obtain super hydrophilic vertical structure
Close polylactic acid membrane.
The invention solves third technical problem be to provide the application of above-mentioned superhydrophilic self-cleaning water-oil separationg film,
The water-oil separating of the oil-in-water emulsion stable for grease stratified mixture or surface-active.
The invention solves the 4th technical problem be to provide it is a kind of improve water-oil separationg film surface hydrophilicity method,
It is covered on the surface of water-oil separationg film and reacts the titanium containing carboxylic acid formed coordinate bond with TiO 2 precursor by plant polyphenol
Super-hydrophilic coating.
Further, the plant polyphenol is the plant polyphenol that ester exchange reaction can occur with TiO 2 precursor；More
Further, the plant polyphenol is the plant polyphenol containing hydroxy or carboxy；Further, the plant polyphenol includes but unlimited
In tannic acid, tea polyphenols, vine polyphenol or gallic acid.
Further, the TiO 2 precursor includes but is not limited to butyl titanate, ethyl alcohol titanium salt or isopropanol titanium salt.
Further, the water-oil separationg film is polylactic acid membrane, polyvinylidene fluoride film, polypropylene screen, cellulose filter membrane or gold
Belong to net.
Further, the method for improving water-oil separationg film surface hydrophilicity are as follows: first by plant polyphenol solution and titanium dioxide
Titanium precursors solution uniformly mixes at 20~40 DEG C, obtains reaction solution after reacting 5~30h；Then by reaction solution using existing
Coating method forms coating in membrane surface；Wherein, the mass ratio of plant polyphenol and TiO 2 precursor is 1:4~10:1.
Further, the method for improving water-oil separationg film surface hydrophilicity are as follows: concentration is more for the plant of 2~8mg/mL
The Tris solution and concentration of phenol are that the alcoholic solution of 0.1~10mg/mL TiO 2 precursor is existed with the volume ratio of 1:1~10:1
It is uniformly mixed at 20~40 DEG C, obtains reaction solution after reacting 5~30h；Use existing coating method in basement membrane table reaction solution again
Face forms coating.
Beneficial effects of the present invention:
(1) present invention utilizes plant polyphenol and titanium dioxide (TiO for the first time2) presoma one-step method membrane surface be made
Super-hydrophilic coating, and then it is prepared for superhydrophilic self-cleaning anti-pollution water-oil separationg film；
(2) in the distilled water or ethyl alcohol of the environment that plant polyphenol is reacted with TiO 2 precursor at room temperature, low energy
Consumption, and it is pollution-free；
(3) plant polyphenol is reacted with TiO 2 precursor one-step method, is swift in response before the reaction to environment nonhazardous,
It is high-efficient, and product is to environment still nonhazardous；
(4) base material can be selected stereocomplex PLA, while degradable have excellent mechanical properties, resistant to hydrolysis,
Solvent resistant, ultraviolet light (UV) radiance provide the foundation for its high use durability degree in practical application in industry；
(5) basement membrane can be is process using the technology of electrostatic spinning, and filametntary diameter, porosity may be implemented
Good control, while electrostatic spinning is a kind of technology that may be implemented to commercially produce, and greatly reduces production cost；
(6) the reacting plant polyphenol and TiO 2 precursor using the method easy to operate such as spin coating, dip-coating, spraying
Object modification is realized in membrane surface from high hydrophobic to super hydrophilic transformation；
(7) due to the stability of super-hydrophilic coating and matrix, obtained super hydrophilic film, which can be realized, is layered a variety of greases
The good separation of the stable oil-in-water emulsion of mixture, surface-active；Simultaneously because the characteristic of electrospun fiber membrane high porosity, it can
To take into account the high permeating flux to water；
(8) during water-oil separating, the membrane material can be inevitably polluted by the oil, under UV illumination, titanium dioxide
Titanium can keep the hydrophily of membrane material, excellent anti-pollution is protected by the greasy dirt photocatalytic degradation on surface at carbon dioxide and water
Demonstrate,prove good cycle performance.
Plant polyphenol selected by the present invention is reacted with TiO 2 precursor one-step method, poly- to such as Stereocomplex to realize
Modification of the water-oil separationg films such as lactic acid film from high hydrophobicity to Superhydrophilic, obtained membrane material can be layered a variety of greases mixed
The stable oil-in-water emulsion of object, surface-active is closed quickly and effectively to separate；Simultaneously under UV illumination, the photocatalytic degradation of titanium dioxide
Characteristic makes film have excellent automatically cleaning anti-pollution, i.e., the film of institute is with good multi-cycle separation performance.It is the pure green, simple
Effectively, inexpensive super hydrophilic film provides a good thinking for water-oil separating processing.
Detailed description of the invention
Fig. 1 is modified stereocomplex PLA film obtained by one gained stereocomplex PLA film of comparative example and embodiment one
FTIR spectrum figure.
Fig. 2 is the SEM figure of modified stereocomplex PLA film obtained by embodiment one, and illustration is contact angle of the film to water.
Fig. 3 is the SEM figure of modified stereocomplex PLA film obtained by comparative example one, and illustration is contact angle of the film to water.
Fig. 4 is the SEM figure of modified stereocomplex PLA film obtained by comparative example two, and illustration is contact angle of the film to water.
Fig. 5 is the SEM figure of modified stereocomplex PLA film obtained by comparative example three, and illustration is contact angle of the film to water.
Fig. 6 is the SEM figure of modified stereocomplex PLA film obtained by comparative example four, and illustration is contact angle of the film to water.
Fig. 7 is the SEM figure of modified stereocomplex PLA film obtained by embodiment two, and illustration is contact angle of the film to water.
Fig. 8 is the SEM figure of modified stereocomplex PLA film obtained by comparative example five, and illustration is contact angle of the film to water.
Fig. 9 is the SEM figure of modified stereocomplex PLA film obtained by embodiment three, and illustration is contact angle of the film to water.
Figure 10 is one~embodiment of embodiment three, is modified stereocomplex PLA film obtained by four~comparative example of comparative example five
To the permeation flux of pure water.
Figure 11 is modified stereocomplex PLA film obtained by embodiment one respectively to chloroform, methylene chloride, n-hexane, first
Benzene, diformazan/water stratification mixed solution separating property.
Figure 12 be modified stereocomplex PLA film obtained by embodiment one to chloroform, methylene chloride, n-hexane, toluene,
The separating property of dimethylbenzene oil-in-water emulsion.
Figure 13 is under the presence or absence of modified stereocomplex PLA film UV light irradiation obtained by embodiment one to oleic acid oil-in-water cream
The separative efficiency of liquid and the performance map of cycle-index.
Specific embodiment
The invention solves first technical problem be to provide a kind of superhydrophilic self-cleaning water-oil separationg film, the grease
Seperation film is the Modified Membrane that membrane surface is covered with super-hydrophilic coating formation；Wherein, the super-hydrophilic coating is plant polyphenol and two
The super-hydrophilic coating of the titania precursor precursor reactant formation coordinate bond of titanium containing carboxylic acid；The basement membrane is the polymerization that can be used for water-oil separating
Object film or non-polymer film.
Second technical problem to be solved by this invention is to provide the preparation of above-mentioned superhydrophilic self-cleaning water-oil separationg film
Method, the preparation method is that: plant polyphenol solution and TiO 2 precursor solution hybrid reaction are first obtained into titanium containing carboxylic acid
The reaction solution of coordinate bond, then reaction solution is formed into super-hydrophilic coating in membrane surface using the method for existing coating；Then through washing
It washs, dry to obtain superhydrophilic self-cleaning water-oil separationg film.
The invention solves third technical problem be to provide the application of above-mentioned superhydrophilic self-cleaning water-oil separationg film,
The water-oil separating of the oil-in-water emulsion stable for grease stratified mixture or surface-active.
The invention solves the 4th technical problem be to provide it is a kind of improve water-oil separationg film surface hydrophilicity method,
It is covered on the surface of water-oil separationg film and reacts the titanium containing carboxylic acid formed coordinate bond with TiO 2 precursor by plant polyphenol
Super-hydrophilic coating.
Following embodiment is several typical embodiments, can not play and limit effect of the invention, this field
Technical staff is referred to embodiment and is reasonably designed technical solution, can equally obtain result of the invention.
Comparative example one
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；It is multiple to obtain high hydrophobic vertical structure
Close polylactic acid membrane.
Embodiment one
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent and obtain mixed liquor,
Mixed liquor is formed a film at 10~20kV with the rate electrospinning of 1mL/h, and then film is annealed 1h at 100~170 DEG C；By 5mg/mL
GA Tris solution ((pH=8)) and 1mg/mL TBT alcoholic solution with the volume ratio of 4:1 after mixing, at 25 DEG C will
12h is reacted in film submergence after annealing in the above solution；Then it is put at 60 DEG C and is dried with after distilled water flushing 1h；I.e.
Obtain super hydrophilic stereocomplex PLA film.
Each embodiment and the modification liquid raw material and its proportion of comparative example, reaction time, contact angle and parent of the gained film to water
It is hydrophobic that the results are shown in Table 1.
Comparative example two
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；Film after annealing is immersed in
In the GA Tris solution of 5mg/mL, in 25 DEG C of reaction 12h；Then it is put at 60 DEG C and is dried with after distilled water flushing 1h；
Obtain hydrophilic stereocomplex PLA film.
Comparative example three
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；Film after annealing is immersed in
In the TBT alcoholic solution of 1mg/mL, in 25 DEG C of reaction 12h；Then it is put at 60 DEG C and is dried with after distilled water flushing 1h；
Obtaining load has TiO2The stereocomplex PLA film of particle.
Comparative example four
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；The GA Tris of 5mg/mL is molten
The TBT alcoholic solution of liquid and 0.5mg/mL after mixing, at 25 DEG C react the film submergence after annealing in the above solution
12h；Then it is put at 60 DEG C and is dried with after distilled water flushing 1h；Obtain hydrophilic stereocomplex PLA film.
Embodiment two
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；The GA Tris of 5mg/mL is molten
Film after annealing after mixing, is immersed in above-mentioned molten by the TBT alcoholic solution of liquid and 5mg/mL with the volume ratio of 4:1 at 25 DEG C
12h is reacted in liquid；Then it is put at 60 DEG C and is dried with after distilled water flushing 1h；It is poly- to obtain super hydrophilic Stereocomplex
Lactic acid film.
Embodiment three
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；The GA Tris of 5mg/mL is molten
Film after annealing after mixing, is immersed in above-mentioned molten by the TBT alcoholic solution of liquid and 1mg/mL with the volume ratio of 4:1 at 25 DEG C
It is reacted for 24 hours in liquid；Then it is put at 60 DEG C and is dried with after distilled water flushing 1h；It is poly- to obtain super hydrophilic Stereocomplex
Lactic acid film.
Comparative example five
By weigh up etc. quality PLLA and PDLA be dissolved in isometric chloroform/hexafluoroisopropanol in the mixed solvent, 10~
It is formed a film under 20kV with the rate electrospinning of 1mL/h, then film is annealed 1h at 100~170 DEG C；The GA Tris of 5mg/mL is molten
Film submergence after annealing is reacted 6h after mixing, at 25 DEG C by the TBT alcoholic solution of liquid and 1mg/mL in the above solution；So
It is put at 60 DEG C and is dried with after distilled water flushing 1h afterwards；Obtain hydrophilic stereocomplex PLA film.
Performance test:
Modified stereocomplex PLA film obtained by one gained stereocomplex PLA film of comparative example and embodiment one carries out
FTIR spectrum detection, detection range is from 4000-450cm-1.One~embodiment of embodiment three and comparative example four, comparative example
The modified stereocomplex PLA film of five gained completes the permeation flux of pure water in the sand core device to test of end-filtration.Embodiment
The modified stereocomplex PLA film of one gained is complete in the sand core device to test of end-filtration to the separation of grease layering mixed solution
Mixed solution is layered at, grease to be obtained by organic solvent/water of isometric ratio being vigorously stirred 3h.It is modified obtained by embodiment one
The separation of the stable oil-in-water emulsion of stereocomplex PLA film Surfactant is complete in the sand core device to test of end-filtration
At the water-organic solvent that oil-in-water emulsion is 1/9 by volume ratio acutely stirs after the surfactant that addition mass ratio is 5ppm
It mixes 5h and obtains.The automatically cleaning anti-pollution of modified stereocomplex PLA film is in each water-oil separating obtained by embodiment one
Afterwards, 3h is irradiated under the UV light of a sunlight intensity, then goes water-oil separating again.
Observe modified stereocomplex PLA film obtained by one gained stereocomplex PLA film of comparative example and embodiment one
FTIR spectrum figure Fig. 1, it can be found that embodiment one several new peaks occurs compared to comparative example one: in 1600-
1450cm-1The peak of appearance is the i.e. absorption peak of GA phenyl ring as caused by C=C stretching vibration on phenyl ring；In 700-500cm-1Out
Existing peak is the i.e. TiO as caused by Ti-O-Ti stretching vibration2Absorption peak；In 3600-3100cm-1The absorption peak of appearance can
Due to being the stretching vibration of hydroxyl, the increase of hydroxyl is derived from the hydroxyl on GA；This shows that GA and TBT is sent out really in the present invention
It has given birth to chemical reaction and has generated modified TiO2, in membrane surface, this can also be demonstrate,proved by the SEM figure of embodiment and comparative example for modification
It is real.
Fig. 2~Fig. 9 is the SME figure of film obtained by the embodiment of the present invention and comparative example, the structure of observation gained membrane material, can be with
It obtains as drawn a conclusion:
Embodiment one all realizes the hydrophily to hydrophobicity sc-PLA film to embodiment three, comparative example four and comparative example five
Modified, contact angle is both less than 65 °, while fiber surface all loads the modified spherical particle of titanium dioxide of GA.By comparative example four, in fact
Apply the SEM figure of two gained film of example one and embodiment as can be seen that with TBT concentration increase, the titanium dioxide of fiber surface by
Cumulative more, matrix surface gradually decreases, until particle begins to block up aperture.By comparative example five, embodiment one, three gained of embodiment
The SEM figure of film can be seen that the growth with the reaction time, show similar trend, the titanium dioxide of fiber surface is gradually
Increase, Severe blockage aperture in last embodiment three.The SEM figure such as Fig. 4 of two gained film of comparative example, it is clearly seen that GA was formed
Sheet plicated layer is wrapped in fiber surface, and forming Stereocomplex fiber is core, the core-shell structure that GA layers are shell, but the contact to water
Angle is 46 °, and super hydrophilic modification is not implemented；The SEM figure of three gained film of comparative example such as Fig. 5, can obviously observe fiber surface
Only a small amount of titanium dioxide granule load, most of particle serious agglomeration is at big spherical, and the contact angle to water is 102 °, not
Realize super hydrophilic modification；But the SEM of one gained film of embodiment figure such as Fig. 2, GA modified titanium dioxide granule uniform close
Ground is carried on sc-PLA fiber surface, is substantially not visible exposed fiber while also no blocking aperture, the contact angle to water are
0 °, realize super hydrophilic modification；In conjunction with FTIR spectrum figure Fig. 9, it was confirmed that GA is reacted with TBT generates super hydrophilic painting
Layer.
The raw material and its proportion of 1 embodiment of table and comparative example, reaction time, contact angle and hydrophilic and hydrophobic to water
Fig. 3 is that the SEM of one gained stereocomplex PLA film of comparative example schemes, and as seen from the figure, fibre diameter is uniform, surface light
Sliding, the contact angle to water is 135 °, shows high hydrophobic property；Fig. 4 is modified stereocomplex PLA obtained by comparative example two
The SEM of film schemes, and as seen from the figure, fiber surface only has GA piece fold package, and the contact angle to water is 46 °, is not carried out super hydrophilic
Modification；Fig. 5 is the SEM figure of modified stereocomplex PLA film obtained by comparative example three, as seen from the figure, TiO2Macro aggregate in fibre
It ties up in layer, fiber surface only has minimal amount of little particle, illustrates TiO2It is difficult to be formed in fiber film surface, the contact angle to water is
102 °, it is not carried out hydrophilic modification；Fig. 6 is the SEM figure of modified stereocomplex PLA film obtained by comparative example four, You Tuke
Know, fiber surface has loaded seldom titanium dioxide granule, and the contact angle to water is 40 °, is not carried out super hydrophilic modification；Figure
7 scheme for the SEM of modified stereocomplex PLA film obtained by embodiment two, and as seen from the figure, fiber surface has loaded much close
Titanium dioxide granule, certain blocking is caused to aperture, is 0 ° to the contact angle of water, realizes super hydrophilic modification；Fig. 8
For the SEM figure of modified stereocomplex PLA film obtained by comparative example five, as seen from the figure, fiber surface has loaded more titanium dioxide
Titanium particle, but without fully wrapped around firmly fiber, the contact angle to water is 27 °, is not carried out super hydrophilic modification；Fig. 9 is to implement
The SEM figure of modified stereocomplex PLA film obtained by example three, as seen from the figure, fiber surface has loaded very fine and close titanium dioxide
Particle, Severe blockage aperture, the contact angle to water are 0 °, realize super hydrophilic modification.
Figure 10 is one~embodiment of embodiment three, is modified stereocomplex PLA film pair obtained by four~comparative example of comparative example five
The permeation flux of pure water；As seen from the figure, the permeation flux highest of embodiment one is 8100Lm-2h-1。
Figure 11 is the processing that the resulting modified stereocomplex PLA film of embodiment one is layered mixed solution to various greases
The research of performance and cycle-index；Mixed solution is layered to the grease of chloroform, methylene chloride, n-hexane, toluene, dimethylbenzene respectively
Separation flux be 7700,7900,9100,7100,7000Lm-2h-1, after multi-cycle separation 20 times, variations of flux is not very big；Table
The stability of one super-hydrophilic coating of embodiment is illustrated.
Figure 12 is the stable various oil-in-waters of the resulting modified stereocomplex PLA film Surfactant of embodiment one
The process performance research of lotion；As shown in Figure 12, one gained membrane material of the embodiment of the present invention to chloroform, methylene chloride, n-hexane,
Toluene, dimethylbenzene oil-in-water emulsion analysis effective percentage be respectively 94.5%, 95.5%, 98.1%, 96.6% and 96.9%, together
When be respectively 7100,6700,8800,6200 and 6500Lm to the permeation flux of water-2h-1；Show that gained membrane material may be implemented
To a variety of oil-in-water emulsion high speeds, efficiently separate.
Figure 13 is that whether there is or not UV light to irradiate after a certain period of time to oleic acid oil-in-water emulsion circulation for the resulting membrane material of embodiment one
Separation Research；As seen from the figure, if being directly separated lotion without UV light irradiation membrane material, the efficient gradually by originating of separation is found
91.1% is reduced to 71.6%, cannot achieve and efficiently separates；On the contrary, membrane material irradiates under w light separates cream again after a certain period of time
Liquid, after 15 circulations, separation effective percentage remains to be maintained at 90% or more for discovery；Prepared membrane material is demonstrated to irradiate in UV light
Under excellent automatically cleaning anti-pollution.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations all should belong to protection scope of the present invention.
Claims (10)
1. a kind of superhydrophilic self-cleaning water-oil separationg film, which is characterized in that the water-oil separationg film is that membrane surface is covered with super parent
The Modified Membrane that water coating is formed；Wherein, the super-hydrophilic coating is that plant polyphenol reacts to be formed containing carboxylic with TiO 2 precursor
The super-hydrophilic coating of sour titanium coordinate bond；The basement membrane is the polymer film or non-polymer film that can be used for water-oil separating.
2. superhydrophilic self-cleaning water-oil separationg film according to claim 1, which is characterized in that
The plant polyphenol is the plant polyphenol that ester exchange reaction can occur with TiO 2 precursor；Further, described
Plant polyphenol is the plant polyphenol containing carboxyl；Further, the plant polyphenol includes but is not limited to tannic acid, tea polyphenols Portugal
Grape polyphenol or gallic acid；Or:
The TiO 2 precursor includes but is not limited to butyl titanate, ethyl alcohol titanium salt or isopropanol titanium salt；Or:
The polymer film that can be used for water-oil separating is polylactic acid membrane, polyvinylidene fluoride film, polypropylene screen or cellulose filter
Film；The non-polymer film that can be used for water-oil separating is metal mesh, preferably copper mesh or iron net.
3. superhydrophilic self-cleaning water-oil separationg film according to claim 1 or 2, which is characterized in that the super-hydrophilic coating
It is made using following methods: plant polyphenol solution is uniformly mixed at 20~40 DEG C with TiO 2 precursor solution, reaction 5
After~30h, reaction solution is formed into super-hydrophilic coating in membrane surface using existing coating method；Wherein, plant polyphenol and two
The mass ratio of titania precursor body is 1:4~10:1；
Further, the super-hydrophilic coating uses following methods to be made: concentration is molten for the Tris of the plant polyphenol of 2~8mg/mL
Liquid and concentration be 0.1~10mg/mL TiO 2 precursor alcoholic solution with the volume ratio of 1:1~10:1 at 20~40 DEG C
Reaction solution after reacting 5~30h, is formed super-hydrophilic coating in membrane surface using existing coating method by uniformly mixing.
4. described in any item superhydrophilic self-cleaning water-oil separationg films according to claim 1~3, which is characterized in that the basement membrane
For polylactic acid membrane；Preferably, the basement membrane is that the mixed solution of l-lactic acid and dextrorotation polylactic acid is formed by electrostatic spinning
Stereocomplex PLA film；
Further, the stereocomplex PLA film the preparation method comprises the following steps: first l-lactic acid is dissolved in dextrorotation polylactic acid molten
Then dosage form passes through method of electrostatic spinning for above-mentioned solution electrospinning into tunica fibrosa at mixed solution；Wherein, the technique item of electrostatic spinning
Part are as follows: the voltage of electrostatic spinning is 5~30kV, and the distance of spinning syringe needle to receiving device is 5~20cm；Preferably, Static Spinning
The voltage of silk is 10~20kV, and the distance of spinning syringe needle to receiving device is 8~18cm；
Further, the mass ratio of the l-lactic acid and dextrorotation polylactic acid is 1:9~9:1, preferably 1:5~5:1, more excellent
It is selected as 1:1.5~3:1；The solvent is at least one in methylene chloride, chloroform, hexafluoroisopropanol or N,N-dimethylformamide
Kind；Preferably, the solvent is the mixed solvent of methylene chloride and hexafluoroisopropanol, the volume of methylene chloride and hexafluoroisopropanol
Than for 1:9~9:1, preferably 1:7~7:1, more preferably 2:7~4:7.
5. the preparation method of the described in any item superhydrophilic self-cleaning water-oil separationg films of Claims 1 to 4, which is characterized in that institute
It states the preparation method comprises the following steps: plant polyphenol solution and TiO 2 precursor solution hybrid reaction are first obtained the coordinate bond of titanium containing carboxylic acid
Reaction solution, then reaction solution is formed into super-hydrophilic coating in membrane surface using the method for existing coating；Then washed, dry
Superhydrophilic self-cleaning water-oil separationg film.
6. the preparation method of superhydrophilic self-cleaning water-oil separationg film according to claim 5, which is characterized in that the preparation
Method are as follows: plant polyphenol solution is uniformly mixed at 20~40 DEG C with TiO 2 precursor solution, it, will after reacting 5~30h
Reaction solution forms super-hydrophilic coating in membrane surface using existing coating method；Then super hydrophilicly from clear washed, dry
Clean water-oil separationg film；Wherein, the mass ratio of plant polyphenol and TiO 2 precursor is 1:4~10:1；
Further, the preparation method is that: by concentration be 2~8mg/mL plant polyphenol Tris solution and concentration be 0.1~
The alcoholic solution of 10mg/mL TiO 2 precursor is uniformly mixed at 20~40 DEG C with the volume ratio of 1:1~10:1, reaction 5
Reaction solution is obtained after~30h；Reaction solution is formed into super-hydrophilic coating in membrane surface using existing coating method again；Then through washing
It washs, dry to obtain superhydrophilic self-cleaning water-oil separationg film.
7. the preparation method of superhydrophilic self-cleaning water-oil separationg film according to claim 6, which is characterized in that when the base
Film is stereocomplex PLA film, and plant polyphenol is gallic acid, when TiO 2 precursor is butyl titanate, the preparation side
Method are as follows: the TiO 2 precursor alcohol for being 1~5mg/mL with concentration by the plant polyphenol Tris solution that concentration is 2~8mg/mL
With the volume ratio of 1:1~10:1,5~30h of uniform hybrid reaction at 20~40 DEG C obtains reaction solution to solution；Basement membrane is immersed in again
In the reaction solution reaction 12~be modified processing for 24 hours；Then by the basement membrane of modification with after distilled water flushing at least 1h,
It is dried at 50~70 DEG C；Obtain superhydrophilic self-cleaning water-oil separationg film.
8. the oil of the superhydrophilic self-cleaning water-oil separationg film oil-in-water emulsion stable for grease stratified mixture or surface-active
Water separation, wherein the superhydrophilic self-cleaning water-oil separationg film is the described in any item superhydrophilic self-cleanings of Claims 1 to 4
Water-oil separationg film uses water-oil separationg film made from the described in any item preparation methods of claim 5~7.
9. it is a kind of improve water-oil separationg film surface hydrophilicity method, which is characterized in that the surface of water-oil separationg film be covered with by
Plant polyphenol reacts the super-hydrophilic coating of the titanium containing carboxylic acid to be formed coordinate bond with TiO 2 precursor；
Further, the plant polyphenol is the plant polyphenol that ester exchange reaction can occur with TiO 2 precursor；Described two
Titania precursor body includes but is not limited to butyl titanate, ethyl alcohol titanium salt or isopropanol titanium salt；The water-oil separationg film is polylactic acid
Film, polyvinylidene fluoride film, polypropylene screen, cellulose filter membrane or metal mesh.
10. the method according to claim 9 for improving water-oil separationg film surface hydrophilicity, which is characterized in that the raising
The method of water-oil separationg film surface hydrophilicity are as follows: first by plant polyphenol solution and TiO 2 precursor solution at 20~40 DEG C
Uniformly mixing obtains reaction solution after reacting 5~30h；Then reaction solution is formed using existing coating method in membrane surface super
Hydrophilic coating；Wherein, the mass ratio of plant polyphenol and TiO 2 precursor is 1:4~10:1；
Further, the method for improving water-oil separationg film surface hydrophilicity are as follows: the plant polyphenol for being 2~8mg/mL by concentration
Tris solution and concentration be the alcoholic solution of 0.1~10mg/mL TiO 2 precursor with the volume ratio of 1:1~10:1 20~
It is uniformly mixed at 40 DEG C, obtains reaction solution after reacting 5~30h；Use existing coating method in membrane surface shape reaction solution again
At super-hydrophilic coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910077498.4A CN109847598B (en) | 2019-01-28 | 2019-01-28 | Super-hydrophilic self-cleaning oil-water separation membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910077498.4A CN109847598B (en) | 2019-01-28 | 2019-01-28 | Super-hydrophilic self-cleaning oil-water separation membrane and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109847598A true CN109847598A (en) | 2019-06-07 |
| CN109847598B CN109847598B (en) | 2021-01-08 |
Family
ID=66896349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910077498.4A Active CN109847598B (en) | 2019-01-28 | 2019-01-28 | Super-hydrophilic self-cleaning oil-water separation membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109847598B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721601A (en) * | 2019-10-09 | 2020-01-24 | 天津工业大学 | Polycaffeic acid/hyperbranched polymer composite nanofiltration membrane as well as preparation method and application thereof |
| CN112023723A (en) * | 2019-07-01 | 2020-12-04 | 江苏久吾高科技股份有限公司 | Hollow fiber membrane and manufacturing method thereof |
| CN112095337A (en) * | 2020-09-17 | 2020-12-18 | 四川大学 | Preparation and application of emulsion separation functional fiber with underwater super-oleophobic property and underwater hydrophilic property |
| CN112322161A (en) * | 2020-09-22 | 2021-02-05 | 山东大学 | Preparation method of super-hydrophilic self-cleaning coating based on cation-pi effect |
| CN114130222A (en) * | 2021-12-15 | 2022-03-04 | 西南石油大学 | Oil-immersed super-hydrophilic multilayer film with microgel structure and preparation method and application thereof |
| CN115445246A (en) * | 2022-08-24 | 2022-12-09 | 电子科技大学 | High-performance surface-modified oil-water separation membrane and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272492A (en) * | 2013-06-19 | 2013-09-04 | 天津工业大学 | Enhanced-cellulose hollow fiber membrane and preparation method thereof |
| CN103328080A (en) * | 2011-06-17 | 2013-09-25 | Lg化学株式会社 | Reverse-osmosis membrane having an ultra-hydrophilic protective layer and method for producing same |
| CN104984666A (en) * | 2015-06-30 | 2015-10-21 | 浙江工业大学 | Metallic polyphenol thin film and preparation method and application thereof |
| CN106139917A (en) * | 2016-08-19 | 2016-11-23 | 杭州易膜环保科技有限公司 | A kind of method of biomimetic modification polyvinylidene fluoride film hydrophilically |
| CN108854591A (en) * | 2018-05-30 | 2018-11-23 | 厦门理工学院 | It is a kind of using tannic acid-titanium as composite nanometer filtering film of separating layer and preparation method thereof |
-
2019
- 2019-01-28 CN CN201910077498.4A patent/CN109847598B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103328080A (en) * | 2011-06-17 | 2013-09-25 | Lg化学株式会社 | Reverse-osmosis membrane having an ultra-hydrophilic protective layer and method for producing same |
| CN103272492A (en) * | 2013-06-19 | 2013-09-04 | 天津工业大学 | Enhanced-cellulose hollow fiber membrane and preparation method thereof |
| CN104984666A (en) * | 2015-06-30 | 2015-10-21 | 浙江工业大学 | Metallic polyphenol thin film and preparation method and application thereof |
| CN106139917A (en) * | 2016-08-19 | 2016-11-23 | 杭州易膜环保科技有限公司 | A kind of method of biomimetic modification polyvinylidene fluoride film hydrophilically |
| CN108854591A (en) * | 2018-05-30 | 2018-11-23 | 厦门理工学院 | It is a kind of using tannic acid-titanium as composite nanometer filtering film of separating layer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XU ZHEFENG, ET AL.: "The film forming mechanism of chromium-free passivation process in the tannic acid system for hot dip galvanizing coating", 《OPTOELECTRONICS AND ADVANCED MATERIALS-RAPID COMMUNICATIONS》 * |
| 张鹏: "聚乳酸电纺纳米纤维结构性能研究与应用拓展", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112023723A (en) * | 2019-07-01 | 2020-12-04 | 江苏久吾高科技股份有限公司 | Hollow fiber membrane and manufacturing method thereof |
| CN110721601A (en) * | 2019-10-09 | 2020-01-24 | 天津工业大学 | Polycaffeic acid/hyperbranched polymer composite nanofiltration membrane as well as preparation method and application thereof |
| CN112095337A (en) * | 2020-09-17 | 2020-12-18 | 四川大学 | Preparation and application of emulsion separation functional fiber with underwater super-oleophobic property and underwater hydrophilic property |
| CN112095337B (en) * | 2020-09-17 | 2021-06-08 | 四川大学 | Preparation and application of emulsion separation functional fiber with underwater super-oleophobic property and underwater hydrophilic property |
| CN112322161A (en) * | 2020-09-22 | 2021-02-05 | 山东大学 | Preparation method of super-hydrophilic self-cleaning coating based on cation-pi effect |
| CN112322161B (en) * | 2020-09-22 | 2022-04-01 | 山东大学 | Preparation method of super-hydrophilic self-cleaning coating based on cation-pi effect |
| CN114130222A (en) * | 2021-12-15 | 2022-03-04 | 西南石油大学 | Oil-immersed super-hydrophilic multilayer film with microgel structure and preparation method and application thereof |
| CN114130222B (en) * | 2021-12-15 | 2023-06-13 | 西南石油大学 | Under-oil super-hydrophilic multilayer film with microgel structure, and preparation method and application thereof |
| CN115445246A (en) * | 2022-08-24 | 2022-12-09 | 电子科技大学 | High-performance surface-modified oil-water separation membrane and preparation method and application thereof |
| CN115445246B (en) * | 2022-08-24 | 2023-10-20 | 电子科技大学 | High-performance surface-modified oil-water separation membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109847598B (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109847598A (en) | A kind of superhydrophilic self-cleaning water-oil separationg film and its preparation method and application | |
| Padmanabhan et al. | Titanium dioxide based self-cleaning smart surfaces: A short review | |
| Yin et al. | A multifunctional and environmentally safe superhydrophobic membrane with superior oil/water separation, photocatalytic degradation and anti-biofouling performance | |
| Ma et al. | Nature-inspired chemistry toward hierarchical superhydrophobic, antibacterial and biocompatible nanofibrous membranes for effective UV-shielding, self-cleaning and oil-water separation | |
| Zhang et al. | Structural design and environmental applications of electrospun nanofibers | |
| Shalaby et al. | Electrospun nanofibers hybrid composites membranes for highly efficient antibacterial activity | |
| Liu et al. | A robust and antibacterial superhydrophobic cotton fabric with sunlight-driven self-cleaning performance for oil/water separation | |
| Pasini et al. | An overview on nanostructured TiO2–containing fibers for photocatalytic degradation of organic pollutants in wastewater treatment | |
| Moatmed et al. | Highly efficient and reusable superhydrophobic/superoleophilic polystyrene@ Fe3O4 nanofiber membrane for high-performance oil/water separation | |
| Yin et al. | Mussel-inspired fabrication of superior superhydrophobic cellulose-based composite membrane for efficient oil emulsions separation, excellent anti-microbial property and simultaneous photocatalytic dye degradation | |
| Li et al. | Influence of Ag/TiO2 nanoparticle on the surface hydrophilicity and visible-light response activity of polyvinylidene fluoride membrane | |
| Ji et al. | Biomimetic hierarchical TiO2@ CuO nanowire arrays-coated copper meshes with superwetting and self-cleaning properties for efficient oil/water separation | |
| Ying et al. | A pre-wetting induced superhydrophilic/superlipophilic micro-patterned electrospun membrane with self-cleaning property for on-demand emulsified oily wastewater separation | |
| Sun et al. | Dopamine-decorated lotus leaf-like PVDF/TiO2 membrane with underwater superoleophobic for highly efficient oil-water separation | |
| Piao et al. | Ultra-low power light driven lycopodium-like nanofiber membrane reinforced by PET braid tube with robust pollutants removal and regeneration capacity based on photo-Fenton catalysis | |
| Kanjwal et al. | Electrospun NiO, ZnO and composite NiO–ZnO nanofibers/photocatalytic degradation of dairy effluent | |
| CN104841015B (en) | High-specific-surface-area silver-loaded titanium dioxide composite antibacterial material and preparation method thereof | |
| CN101785976A (en) | Polymer separation membrane with on-line antibiosis and self-cleaning functions and preparation method thereof | |
| Wang et al. | In-situ formation of durable akaganeite (β-FeOOH) nanorods on sulfonate-modified poly (ethylene terephthalate) fabric for dual-functional wastewater treatment | |
| Skorb et al. | Photocatalytically-active and photocontrollable coatings based on titania-loaded hybrid sol–gel films | |
| Shan et al. | Flexible, mesoporous, and monodispersed metallic cobalt-embedded inorganic nanofibrous membranes enable ultra-fast and high-efficiency killing of bacteria | |
| Kanjwal et al. | Photocatalytic degradation of dairy effluent using AgTiO2 nanostructures/polyurethane nanofiber membrane | |
| Görgülüer et al. | Ag NPs deposited TiO2 coating material for superhydrophobic, antimicrobial and self-cleaning surface fabrication on fabric | |
| Sun et al. | Multi-scaled, hierarchical nanofibrous membrane for oil/water separation and photocatalysis: Preparation, characterization and properties evaluation | |
| CN106110901A (en) | A kind of antibacterial antifouling oil-water separation material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |